Preparation of tertiary butyl phenol



- Patented Aug; 31, 1937 UNITED STATES PREPARATION OF TERTIARY BUTYL PHENOL Ralph P. Perkins and Howard S. Nutting, Midland, Mich assignors to The Dow Chemical Company, Midland, Mich, a corporation of Michigan No Drawing. Application July 15, 1935, Serial No. 31,444

11 Claims.

This invention concerns a method of preparing tertiary butyl phenol.

It is well known that an'alkylated aromatic compound, such as an alkyl phenol, can be preby heating tertiary octyl phenol, e. g., the product of Equation 1, with phenol under like conditions, i. e. at a temperature above 90 C. in the presence of a catalyst, tertiary butyl phenol is formed in accordance with Equations (2) and (3). There is thus afforded a method whereby diand tri-p isobutylenes, which may be.produced in large quantities from lay-product materials in the cracking of petroleum, may be utilized in the produc tion of the commercially-valuable compound,

tertiary butyl phenol. The invention, then, consists in the method of making tertiary butyl phenol hereinafter fully described and particularly pointed out in the claims.

5 pared by reacting the aromatic compound with In preparing tertiary butyl phenol from di- 5 an olefine corresponding to the alkyl group to be isobutylene and phenol by our method, a mixture introduced into the aromatic ring in the presence of said compounds is heated to a reaction tem- -of a Friedel-Crafts catalyst. For instance, in perature above 90 0., preferably between 110 Annales de Chimie, Ser. 10, vol. 11, pages 550556, and 190 C., in the presence of a Friedel-Crafts the reaction of cyclohexene with phenol to produce catalyst. The di-isobutylene and phenol may be 10 cyclohexyl phenol is described. Also, in a coemployed in any desired proportions, but the pending application of Ralph P. Perkins, Serial reaction proceeds most satisfactorily when an ex- No. 737,813, filed July 31, 1934, it is disclosed that cess of the phenol is employed. Likewise, the

r a polyolefine, e. g. di-isobutylene, may be reacted catalyst may be employed in any desired propor- 10 with phenol in the presence of a Friedel-Crafts .tion, but, for the sake of economy, is preferably catalyst at a temperature below 90 C. to produce used in a proportion representing between about the correspondingalkylated phenol, i; e., tertiary 1 per cent and about 10 per cent of the weight octyl phenol, in good yield. of the phenol. Among the various Friedel-Crafts 'We have now discovered that by reacting a polycatalysts which may be used are aluminum chloisobutylene, e. g., di-isobutylene, tri-isobutylene, ride, aluminum bromide, ferric chloride, stannic 20 etc., or mixtures thereof, with phenol at a tem-' chloride, or an acid-activated bleaching earth perature above 90 C., tertiary butyl phenol insuch as tonsil, super-filtrol, etc. The reaction is stead of tertiary octyl phenol is formed as the usually carried out under reflux at atmospheric major product. Apparently, the types of reacpressure, but may be carried out under elevated tions involved are illustrated by the following pressures in a closed reactor, if desired. The reequations for the production of tertiary butyl action is usually complete after from 1 to 3 hours phenol from di-isobutylene and phenol: of heating, but a longer heating period may some- Ha OH: H: CH3

Di-isobutylene Phenol Tertiary octyl phenol CH3 OH: H: CH3

Tertiary octyl phenol Tertiary butyl phenol Isobutylene on: 40 a CHFCZCHQ-I-CGEHOH H;C--CCi 4 40 CH3 CH3 Isobutylene Phenol Tertiary butyl phenol This is confirmed by our further discovery that times be required, particularly when a mildly active catalyst such as acid-activated siliceous earth is employed.

After completing the reaction, the mixture is cooled and the catalyst removed or destroyed by usual procedure, e. g., by treatment with water, an aqueous base, or an aqueous acid solution. The mixture is then distilled to separate the tertiary butyl phenol product.

Instead of preparing tertiary butyl phenol by reacting di-isobutylene with phenol as described above, the compound may be produced equally well by heating tertiary octyl phenol to a temperature above 90 C. with, preferably, one or more times its molecular equivalent of phenol, in

5 the presence of a Friedel-Crafts catalyst. The

reactions involved are set forth in Equations (2) and (3) above.

The following examples illustrate several ways in which the principle of our invention is being employed, but are not to be construed as limiting the invention.

' Example 1 1410 grams moles) of phenol and 45 grams of aluminum chloride were stirred together, and to this solution was added 560 grams (5 moles) of di-isobutylene, during a period of 45 minutes, the solution temperature being held between 85-90 C. The reaction mixture was then heated to a temperature of approximately 120 C., which temperature was maintained for 2 hours. The resultant product was neutralized with aqueous sodium carbonate, filtered, and the filtrate was distilled. There was obtained 593 grams of unreacted phenol and 967 grams of para-tertiary butyl phenol, having a freezing point of 972 C. The yield of para-tertiary butyl phenol was 64.5 per cent of theoretical, based on the quantity of phenol reacted.

Example 2 To a mixture of 282 grams (3 moles) of phenol with 112 grams (1 mole) of di-isobutylene was added 2.8 grams of tonsil. The resultant solution was heated under refiux at temperatures between 170 and 182 c. for two hours. The mixture was then filtered and the filtrate fractionally distilled under vacuum, whereby there was obtained 128.5 grams of unreacted phenol and 170 grams of para-tertiary butyl phenol. The yield 40 of para-tertiary butyl phenol was 69.5 per cent of theoretical, based on the phenol reacted.

Example 3 8 grams of tonsil and 168 grams of a poly- Example 4 To 376 grams (4 moles) of phenol was added 18.8 grams of anhydrous aluminum chloride and 206 grams (1 mole) of para-tertiary octyl phenol. This mixture was heated with agitation at 117- 123 C. for one-half hour. Thereafter the temperature was reduced to 90 C. and the reaction mixture neutralized by adding an aqueous sodium carbonate mixture containing 31 grams of sodium carbonate and 62 grams of water. The mixture was then filtered and the filtrate fractionally 65 distilled under vacuum. There was obtained 309 grams of unreacted phenol and 169 grams (1.13 moles) oi. para-tertiary butyl phenol.

The reactions herein described for the production of tertiary butyl phenol may, ii desired, be carried out in the presence of a relatively nonreactive diluent such as carbon bisulphide, benzene, toluene, xylene, etc., but ordinarily we prefer to carry said reactions out in the absence of solvents other than the reactants themselves.

2. In a method of making tertiary butyl phe-- nol, the step which consists in heating a mixture of phenol and di-isobutylene toa reaction temperature between and C. in the presence of a Friedel-Grafts catalyst in amount representing between about 1 per cent and about 10 per cent of the weight of the phenol.

3. In a method of making tertiary butyl'phenol, the steps which consist in treating phenol with at least 1 per cent its weight of a Friedel- Crafts catalyst, adding di-isobutylene and heating the mixture to a, reaction temperature between about 110 and about 190 C.

4. In a method of making. tertiary butyl phenol, the step which consists in heating a mixture 01' phenol and tertiary octyl phenol to a reaction temperature between 110 and 190 C. in the presence of a catalyst in amount representing at least 1 per cent of the weight of the phenol.

5. In a method of making tertiary butyl phenol, the step which consists in reacting a polymerized isobutylene mixture with phenol at a temperature between 110 and 190 C. in the presence of a Friedel-Crafts catalyst.

6. In a method of making tertiary butyl phenol, the step which consists in reacting a polyisobutylene with phenol in the presence of aluminum chloride at a. temperature between about 110 and about 190 C.

7. In a method of making tertiary butyl phenol, the step which consists in reacting di-isobutylene with phenol in the presence of aluminum chloride at a temperature between about 110 and about 190 0.

8. In a method of making tertiary butyl phenol, the step which consists in reacting a polyisobutylene with phenol in the presence of an acid-activated bleaching earth at a temperature between about 110 and 190 C.

9. In' a method of making tertiary butyl phenol, the step which consists in reacting di-isobutylene with phenol in the presence of an acidactivated bleaching earth at a temperature be tween about 110 and 190 C.

10. The method which comprises reacting phenol with a poly-isobutylene at a temperature 

